Preparation of alcohols from synthesis gas

ABSTRACT

An alcohol mixture suitable for combining with gasoline is produced by contacting synthesis gas at elevated temperature and pressure with an oxide complex catalyst containing copper, thorium, an alkali metal and at least one other specific element.

This application is a continuation of application Ser. No. 503,076,filed June 13, 1983 (now abandoned), which was a continuation ofapplication Ser. No. 393,829, filed June 30, 1982 (now abandoned), whichwas a continuation of application Ser. No. 054,216, filed July 2, 1979(now abandoned), which was a continuation of application Ser. No.905,703, filed May 15, 1978 (now abandoned). The disclosures of theseprior applications are incorporated herein by reference in theirentirety.

BACKGROUND OF THE INVENTION

The present invention relates to a new process for making alcoholmixtures preferably containing no more than 85% methanol and to gasolinecompositions containing such alcohol mixtures.

It is well known to incorporate methanol into gasoline for the purposeof increasing the amount of useful fuel obtained. Unfortunately, thepresence of a small amount of water in a methanol/gasoline mixturecauses separation of the methanol and gasoline phases. In order toovercome this problem, higher alcohols can be added to methanol/gasolinemixtures, such compositions being able to tolerate a much greater amountof water than a simple methanol/gasoline mixture. See U.S. Pat. Nos.3,832,149, 3,822,119 and 2,128,910. Higher alcohols can also be usedalone. See U.S. Pat. No. 2,078,736.

Although it has been known for many years that alcohols can beincorporated into gasolines, most gasolines made at this time contain noalcohols, and this is due primarily to economic reasons.

It has also been long known to prepare alcohols by catalyticallyreacting carbon monoxide and hydrogen together using catalysts which maycontain copper and thorium. See, for example, U.S. Pat. Nos. 1,707,331,2,061,470, 2,500,913, 1,741,307, 1,625,929 and 1,831,179. Suchprocesses, however, normally require extremely high reactiontemperatures and pressures and hence have not been employed commerciallyto any significant extent.

Accordingly, it is an object of the present invention to provide asimple, straightforward and very inexpensive process for producingalcohol mixtures for incorporating into gasoline.

In addition, it is a further object of the present invention to providea novel alcohol mixture and in addition a gasoline compositioncontaining this novel alcohol mixture.

SUMMARY OF THE INVENTION

These and other objects are accomplished by the present invention inaccordance with which a mixture of methanol and higher alcohols isproduced by contacting synthesis gas with a novel copper/thorium/alkalimetal oxide catalyst. Alcohol compositions produced by this procedurecontain a unique distribution of alcohols having 2 to 6 carbon atoms andnormally not more than 85% methanol by weight. These compositions can bedirectly admixed with gasoline to provide a new gasoline compositioncontaining a mixed alcohol system which will not separate from theremainder of the gasoline even in the presence of significant amounts ofwater.

Thus, the present invention provides a unique process for producingalcohol mixtures, the inventive process comprising contacting a gaseousreactant containing carbon monoxide and hydrogen with an oxide complexcatalyst described by the formula

    Cu.sub.a ThM.sub.b A.sub.c O.sub.x

wherein

M is one or more of Ca, Mo, Rh, Mn, Pt, Ce, Cr, Zn, Al, Ti, La, V, U,Ru, Re and Pd;

A is an alkali metal; and

wherein

a is 0.5 to 2.5;

b is 0.01 to 1.0;

c is 0.05 to 0.9; and

x is a number such that the valence requirements of the other elementsfor oxygen is satisfied.

In addition, the present invention further provides a novel alcoholcomposition suitable for admixing with gasoline, the alcohol compositionbeing composed of C₂ and higher alcohols having an alcohol distributionas follows:

C₂ --4-25%

C₃ --0.1-25%, preferably 9-25%

C₄ --0.5-70%, preferably 40-70%

C₅ --0.1-12%

C₆ --0.1-10%

C₆ --0.1-10%

the percents being based on the weight of the total amount of alcoholsin the mixture having two or more carbon atoms. Normally, this alcoholcomposition will also contain methanol, usually in amounts of 40 to 85%although the methanol content may range from 0 to 92% or more.

Furthermore, the present invention also provides a novelalcohol/gasoline composition comprising a homogenous solution ofgasoline and the novel alcohol composition of the present invention.

DETAILED DESCRIPTION Reactants

The material being reacted in accordance with the present invention toform alcohols is preferably synthesis gas. As is well known, synthesisgas is composed basically of a mixture of hydrogen and carbon monoxidein which the H₂ /CO ratio is from 0.6 to 6, more normally between 1 and2. It is normally derived by heating coke in the presence of air andthen steam. Alternately, it can also be produced by partial combustionof coal, natural gas or petroleum hydrocarbons. It is sometimes referredto as "water gas." Synthesis gas normally contains a very low amount ofsulfur compounds. It also may contain small amounts of carbon dioxide,nitrogen and other inerts.

Although synthesis gas is a preferred reactant, any other gas composedprimarily of hydrogen and carbon monoxide and having an H₂ /CO ratio of0.6 to 6 can be employed. The gaseous reactant should contain as littlesulfur compounds as possible since sulfur is a known poison for coppercontaining catalysts when used in conventional methanol synthesis.Preferably the gaseous reactant is essentially sulfur-free.

Reaction Mode and Conditions

The inventive process is carried out by contacting the gaseous reactantwith the inventive catalyst as described below in a suitable reactor.The reaction can be carried out either in fluid-bed mode or fixed-bedmode, continuously or in batch operation.

The contact time of the reactants with the products is not critical butshould be below about 200 seconds and preferably between about 35 and135 seconds.

The reaction pressure should normally be between 500-1500 psi and ispreferably between 750-1000 psi. Although there is no real upper limitto the reaction pressure, pressures higher than 1500 psi are normallynot employed because of the high expense involved. Also, pressures aslow as 250 psi can be employed, although it is preferable to operate atat least about 500 psi because formation of alcohols is favored athigher pressures.

The reaction temperature should be maintained between about 200°-425°C., preferably 250°-350° C., and most preferably 280°-330° C. Thereaction temperature, like the reaction pressure, is not particularlycritical, although a marked decrease in conversion rates will beobtained if temperatures and pressures lower than 250 psi and 200° C.are employed. Also, the amount of methanol in the reaction productincreases with practically all catalysts when the reaction temperaturedrops below about 200° C. It will be noted that temperatures andpressures employed in this process are quite a bit lower thantemperatures and pressures necessary in prior art processes forproducing mixed alcohols from synthesis gas.

Catalyst

The catalyst employed in the inventive process is believed to be anoxide complex and can be described by the empirical formula:

    Cu.sub.a ThM.sub.b A.sub.c O.sub.x

wherein

M is one or more of Ca, Mo, Rh, Mn, Pt, Ce, Cr, Zn, Al, Ti, La, V, U,Ru, Re or Pd, preferably Cr, Zn, Al, Ti, La, V or Pd;

A is an alkali metal, preferably Na; and

wherein

a is 0.5 to 2.5, preferably 1.3 to 1.7;

b is 0.01 to 1.0, preferably 0.01 to 0.6;

c is 0.05 to 0.9, preferably 0.225 to 0.55; and

x is a number such that the valence requirements of the other elementsfor oxygen is satisfied.

These catalysts can be prepared by a procedure involving adding analkali metal carbonate to an aqueous solution containing decomposablesalts of thorium, copper and the "M" element, to form a precipitateheating the precipitate in its mother liquor for a suitable time,neutralizing the precipitate, drying the precipitate and thereaftercalcining and then reducing the precipitate.

More specifically, the catalysts of the present invention can beprepared by the following procedure:

(1) A solution preferably aqueous, containing decomposable salts ofthorium, copper and the "M" element is first formed. Nitrates arepreferably used as the decomposable salts, although salts having otherdecomposable anions such as acetates, propionates, benzoates, acetylacetonates, naphthenates, chlorides and the like can be employed.

(2) To the aqueous salt solution is added alkali metal carbonate,preferably also in the form of an aqueous solution. During thisaddition, the admixture is preferably maintained at an elevatedtemperature, e.g. 80°-95° C. As the alkali metal carbonate is added tothe salt solution, carbon dioxide is evolved and a sky-blue precipitatewhose exact nature is unknown begins to form. Addition of alkali metalcarbonate is continued while maintaining the temperature of the systempreferably between 80°-95° C. until the pH of the system, which isinitially at about 1, increases to at least 7.5, preferably at least 8,preferably about 9.3-10. At this time a gelatinous sky-blue precipitatein significant amount has been formed. An alkali metal hydroxide can beused in place of the carbonate, although the carbonate is preferredbecause it gives better results.

(3) This gelatinous precipitate is then allowed to digest in its motherliquor while the temperature of the system is maintained at its elevatedvalue, preferably 80°-95° C. During this time, it will be noted that thecolor of the precipitate undergoes a significant change from sky-bluethrough green through brown to nearly black.

(4) When no more color change occurs, an acid, preferably nitric acid,is added to bring the pH to about neutral, preferably 6.8-7, which isbelieved to cause precipitation of any dissolved Cu remaining in themother liquor. The precipitate is then filtered and washed with wateruntil the alkali metal content of the finished catalyst falls to thedesired value. This can be easily determined by trial and error.

(5) The precipitate is then dried at a convenient temperature, forexample 120° C., and then calcined for a time and at a temperaturesufficient to drive out the remaining water in the precipitate anddecompose decomposable ions remaining in the precipitate, such asnitrates and carbonates. Temperatures of 250°-500° C., preferably350°-450° C. for periods of 30 minutes to about 5 hours have been foundsufficient for this purpose.

(6) Since the catalyst of the present invention is used in a reducingatmosphere, it is preferable to reduce the calcined precipitate prior touse in the inventive process. Prereduction of the catalyst, however, isnot necessary, since the catalyst will automatically undergo reductionto an equilibrium value in use, although the activity of the catalystmay not be as great as when a proper prereduction procedures is carriedout. In this regard, it is believed that heating of the calcinedprecipitate to higher temperatures will cause significant reduction inthe activity of the ultimate catalyst produced due to sintering ofparticles of the calcined precipitate. Since a very exothermic reactionmay occur when a reducing gas is contacted with the calcinedprecipitate, it is preferable to subject the calcined precipitate to acontrolled reduction procedure in order to avoid heating the calcinedprecipitate to above 300° C. Therefore, it is preferable to carry out acontrolled reduction of the calcined precipitate in the followingmanner, although any other satisfactory technique could be employed aswell.

The calcined precipitate is first heated under inert atmospherepreferably in the alternate reaction vessel to a temperature of about200° C. Next, an inert gas containing a low concentration (e.g. about5%) of a reducing gas, preferably H₂ although a mixture of H₂ and CO canbe employed, is admitted to the gas surrounding the catalyst for initialreduction of the metal and concomitant heat evolution. Thereafter, theconcentration of the reducing gas is slowly increased to 100%, carebeing taken to keep the rate of reducing gas applied low enough toprevent the temperature of the catalyst from exceeding a value at whichsignificant sintering occurs, usually about 300° C. Once 100% reducinggas is reached, the pressure in the reaction vessel is slowly increasedto the desired reaction pressure, the catalyst new being ready toreceive reactant.

The catalysts of the present invention can be used alone or supported onvarious inert supports such as silica, alpha-alumina, Alundum, mulliteand the like. These materials are preferably low surface area supportsand can be added to the catalyst during its preparation (i.e. after thesky-blue precipitate is first formed) or after the preparation of thecatalyst in conventional manners.

Product

The composition produced by the inventive process is a mixture ofalcohols containing methanol predominantly as well as significant amountof higher alcohols usually having 2-8 carbon atoms. Normally, thealcohol product of the present invention will contain 40-85% methanol,although higher amounts of methanol may be included in the product ifreaction temperature is too low, if the catalyst is calcined at too higha temperature or if the catalyst contains additional elements fosteringthe generation of higher amounts of methanol than normal.

In this regard, it has been found that the amount of methanol in theproduct alcohol mixture will usually exceed 85% if the M element in thecatalyst is chosen as Ca, Mo, Rh, Mn, Pt, Re, Ru or in some instancesCe. For this reason, Cr, Zn, Al, Ti, La, V and Pd are preferred as the Melement. In any event, an alcohol mixture produced by the inventiveprocess and containing over 85% methanol can also be directly added togasoline as is. It is preferable, however, to distill off excessmethanol so that the methanol content of the alcohol mixture is no morethan 85%.

The portion of the alcohol product other than methanol is a mixturecomposed substantially completely of 2-6 carbon atom alcohols, This C₂-C₆ alcohol mixture has an alcohol distribution scheme as given in thefollowing Table I.

TABLE I

C₂ --4-25%

C₃ --0.1-25%, preferably 9-25%

C₄ --0.5-70%, preferably 40-70%

C₅ --0.1-12%

C₆ --0.1-10%

C₆ --0.1-10%

the percents being based on the weight of the total amount of alcoholsin the products having 2 or more carbon atoms. These alcohols arecomposed almost completely of isoalcohols and normal alcohols with theiso/normal ratio being about 0.7 to 2. Substantially no tertiaryalcohols are present.

Gasoline

The product alcohol mixtures of the present invention (whethercontaining more or less than 85% methanol) are useful in expandinggasoline. They can be mixed with gasoline in any amount, and whenpresent in amounts of less than 25% no significant effect on theoperation of an internal combustion engine containing thegasoline/alcohol mixture will be noticed. Furthermore, the mixed alcoholproducts of the present invention can be mixed with any type of gasolinebe it substantially all paraffinic such as alkylate or highly aromatic.Moreover, if the product alcohol mixture employed has no more than 85%methanol, the resultant gasoline will be able to tolerate significantamounts of water without phase separation.

SPECIFIC EMBODIMENTS

In order to more thoroughly describe the present invention, thefollowing specific examples are provided.

Catalyst Preparation EXAMPLE 1 Cu₁.5 ThPd₀.05 Na_(y) O_(x)

To 660 cc of distilled water were added 60.66 grams of Cu(NO₃)₂.21/2H₂ Oand 95.99 grams of Th(NO₃)₄.4H₂ O. The nitrates were dissolved bywarming with stirring, and then 1.54 grams of PdCl₂ were disolved in thenitrate solution. The nitrate solution was heated to 90° C., and withhigh speed stirring there was added a hot (90°-95° C.) solution of 73.2grams of Na₂ CO₃ in 800 cc of distilled H₂ O. Using a pH meter,sufficient additional Na₂ CO₃ was added to bring the pH of the slurry to9.5. Heating was continued until the color change to dark brown wascomplete, about half of the water being evaporated. The slurry was thencooled to room temperature, and the pH adjusted to 7.0 with a 20% HNO₃solution. The slurry was filtered using vacuum, and sucked as dry aspossible. The filter cake was washed three times by re-slurrying in 800cc of distilled H₂ O at 60°-70° C., and refiltering. It was then driedapproximately 16 hours at 120° C., and calcined 3 hours at 275° C. and16 hours at 350° C. in air. The sodium content of the finished catalystwas 1.6 weight %.

EXAMPLE 2 Cu₁.5 ThCr₀.3 Na_(y) O_(x)

The procedure of Example 1 was followed except that 20.9 grams ofCr(NO₃)₃.9H₂ O rather than 1.54 grams PdCl₂ was dissolved in thecopper-thorium nitrate solution. The final catalyst contained 0.55weight % Na.

EXAMPLE 3 Cu₁.5 ThLa₀.15 Na_(y) O_(x)

The procedure of Example 1 was followed except that 11.3 grams ofLa(NO₃)₃.6H₂ O rather than the PdCl₂ was added to the copper-thoriumnitrate solution. In addition, the final catalyst contained 1.45 weight% Na.

EXAMPLE 4 Cu₁.15 ThCe₀.30 Na_(y) O_(x)

The procedure of Example 1 was followed except that 22.6 grams ofCe(NO₃)₃.6H₂ O rather than the PdCl₂ was added to the copper-thoriumnitrate solution. In addition, the catalyst contained 0.9 weight % Na.

EXAMPLE 5 Cu₁.5 ThTi₀.15 Na_(y) O_(x)

The procedure of Example 1 was followed except that in place of thePdCl₂ 2.1 grams of TiO₂ were suspended in the copper-thorium nitratesolution before precipitation. The catalyst contained 0.68% Na.

EXAMPLE 6 Cu₁.5 ThZn₀.15 Na_(y) O_(x)

78 grams of Cu(C₂ H₃ O₂)₂.H₂ O, 144 grams of Th(NO₃)₄.4H₂ O and 4.78grams of ZnO in 1 liter of water were heated to 90° C. Precipitation wasdone with a hot solution of 117.3 grams Na₂ CO₃ in 1.2 liters of H₂ O.The pH was adjusted to 9.8 with additional Na₂ CO₃. The balance of thepreparation was accomplished in the same manner as set forth above inconnection with Example 1.

EXAMPLE 7 Cu₁.5 ThAl₀.15 Na_(y) O_(x)

In 1 liter of distilled water were dissolved 94.5 grams Cu(NO₃)₂.3H₂ O,144 grams of Th(NO₃)₄.4H₂ O and 22.0 grams of Al(NO₃)₃.9H₂ O, and thesolution was heated to 90° C. This was added to a solution of 170.4grams of Na₂ CO₃ in 1.2 liters of distilled H₂ O and heated to 90°-95°C. The pH of the slurry was adjusted to 9.5 with additional Na₂ CO₃. Theremainder of the preparation was carried out in the same manner as setforth above in connection with Example 1. The catalyst contained 1.47weight % Na.

EXAMPLE 8 Cu₁.0 Th₁.0 Pd₀.05 Na_(y) O_(x)

The procedure of Example 1 was repeated except that 1.95 grams of Pd(C₃H₈ O₂)₂ were employed in place of the PdCl₂ of Example 1. Also, thesodium content of the catalyst obtained was 1.28 weight %.

EXAMPLE 9 Cu₁.0 Th₁.0 U₀.2 Na_(y) O_(x)

The procedure of Example 1 was repeated using 58.9 grams Cu(NO₃)₂.3H₂ O,134.6 grams Th(NO₃)₄.4H₂ O and 24.5 grams (UO₂)(NO₃)₂.6H₂ O dissolved in600 cc of water to form the aqueous salt solution. The catalystcontained 1.6% Na.

EXAMPLE 10 CuThCr₀.15 Na_(y) O_(x)

The procedure of Example 1 was repeated except that 94.5 g Cu(NO₃)₂.3H₂O, 144 g Th(NO₃)₄.4H₂ O and 23.5 g Cr(NO₃)₃.9H₂ O in distilled waterwere used and in addition 119.1 gm Na₂ CO₃ in 1 liter of water was used.The catalyst obtained contained 1.0% Na.

EXAMPLE 11 CuThCe₀.15 Na_(y) O_(x)

The procedure of Example 10 was repeated except that 25.5 gmCe(NO₃)₃.6H₂ O and 120 gm Na₂ CO₃ in 2 liters water were used. Thecatalyst contained 1.21% Na.

Alcohol Production EXAMPLES 12 TO 22 AND COMPARATIVE EXAMPLES A AND B

A series of experiments was run in order to determine the catalyticactivity of the various catalysts prepared in Examples 1-11 in theproduction of alcohol mixtures. In each experiment, 40 cc of catalystwas charged into a fixed-bed reactor and contacted with an H₂ /COmixture having an H₂ /CO ratio of approximately 1/1. The processes werecarried out at a temperature of 288° C., a pressure of 750 psig and acontact time of 52 seconds. The results obtained are tabulated in thefollowing Tables II and III.

EXAMPLES 23 TO 33

Additional experiments were conducted using the same conditions as inExamples 12 to 22. The catalysts used in these experiments are describedby the general formula.

    Cu.sub.1.5 ThM.sub.b NaO.sub.x

with the M_(b) member of each catalyst and the results obtained beingset forth in the following Table IV.

                                      TABLE II                                    __________________________________________________________________________    Percent Yield of Methanol and Higher Alcohols                                                            Product                                                               % Yield*                                                                              Composition (Wt.%)                                 Example                                                                            Catalyst Composition                                                                        Alcohols                                                                           CO.sub.2                                                                         MeOH                                                                              C.sub.2+  Alcohols                                                                   C.sub.1 /C.sub.2+  Alcohol              __________________________________________________________________________                                          Ratio                                   12   Cu.sub.1.5 ThPd.sub.0.05 Na.sub.y O.sub.x                                                   19.2 11.3                                                                             67.1                                                                              30.7   2.2                                     13   Cu.sub.1.5 ThCr.sub.0.3 Na.sub.y O.sub.x                                                    16.5 10.9                                                                             83.5                                                                              15.0   5.6                                     14   Cu.sub.1.5 ThLa.sub.0.15 Na.sub.y O.sub.x                                                   15.9 10.9                                                                             83.4                                                                              15.6   5.3                                     15   Cu.sub.1.5 ThCe.sub.0.3 Na.sub.y O.sub.x                                                    16.1 13.3                                                                             75.8                                                                              23.1   3.3                                     16   Cu.sub.1.5 ThTi.sub.0.15 Na.sub.y O.sub.x                                                   15.3 11.0                                                                             84.4                                                                              15.3   5.5                                     17   Cu.sub.1.5 ThZn.sub.0.15 Na.sub.y O.sub.x                                                   17.1 9.0                                                                              77.7                                                                              18.1   4.3                                     18   Cu.sub.1.5 ThA1.sub.0.15 Na.sub.y O.sub.x                                                   13.9 9.1                                                                              84.0                                                                              15.1   5.6                                     19   Cu.sub.1.5 ThPd.sub.0.05 Na.sub.y O.sub.x                                                   19.5 11.5                                                                             64.6                                                                              33.0   2.0                                     20   Cu.sub.1.0 ThU.sub.0.2 Na.sub.y O.sub.x                                                     4.91 3.34                                                                             91.5                                                                              8.5                                            21   Cu.sub.1.5 ThCr.sub.0.15 Na.sub.y O.sub.x                                                   15.8 8.6                                                                              78.8                                                                              21.1   3.7                                     22   Cu.sub. 1.5 ThCe.sub.0.15 Na.sub.y O.sub.x                                                  17.4 9.8                                                                              77.8                                                                              21.1   3.7                                     A    Cu.sub.0.51 ZnAl.sub.0.760 O.sub.x                                                          14.4 7.3                                                                              93.5                                                                              5.9    15.8                                         (commercial MeOH catalyst)                                               B    Cu.sub.0.51 ZnAl.sub.0.760 + 2.5% Na                                                        15.9 5.8                                                                              93.4                                                                              6.3    14.8                                    __________________________________________________________________________     insert                                                                   

                                      TABLE III                                   __________________________________________________________________________    Distribution of Alcohols in Product                                           Experiment No.                                                                              12  13   14  15  16   17   18  19   20  21  22                  __________________________________________________________________________    M.sub.b       Pd.sub.0.05                                                                       Cr.sub.0.3                                                                         La.sub.0.15                                                                       Ce.sub.0.3                                                                        Ti.sub.0.15                                                                        Zn.sub.0.15                                                                        Al.sub.0.15                                                                       Pd.sub.0.05                                                                        U.sub.0.2                                                                         Cr.sub.0.15                                                                       Ce.sub.0.15         Liquid Analysis, Wt. %                                                        methanol      67.1                                                                              83.5 83.4                                                                              75.8                                                                              84.4 77.7 84.0                                                                              64.6 92.2                                                                              78.8                                                                              77.8                ethanol       3.5 1.7  1.8 1.1 1.2  2.7  2.4 3.1  1.9 1.8 1.5                 acetone       0.4 0.5  0.5 --  0.6  0.3  0.4 0.7  --  0.6 0.6                 iso-C.sub.3 OH                                                                              1.0 0.5  0.6 1.3 0.4  0.7  0.7 0.9  0.1 0.7 0.7                 n-C.sub.3 OH  4.7 1.4  1.5 0.9 0.9  1.6  2.1 3.9  0.4 2.3 1.6                 sec-C.sub.4 OH                                                                              0.7 1.1  0.7 1.5 1.1  0.4  0.6 1.3  --  0.9 1.1                 iso-C.sub.4 OH                                                                              12.2                                                                              6.8  7.0 13.6                                                                              8.4  7.3  6.4 15.2 0.5 10.6                                                                              10.9                n-C.sub.4 OH  2.2 1.3  1.3 1.8 1.3  1.4  0.7 2.6  0.04                                                                              1.3 1.7                 iso-C.sub.5 OH                                                                              0.7 0.1  0.2 --  trace                                                                              0.5  0.4 0.5  0.06                                                                              0.8 0.4                 n-C.sub.5 OH  2.8 0.7  1.2 1.7 trace                                                                              1.7  1.1 2.4  0.07                                                                              1.3 1.2                 iso-C.sub.6 OH                                                                              0.5 0.2  0.2 0.1 0.8  0.3  0.1 0.5  --  0.2 0.3                 n-C.sub.6 OH  1.8 0.7  0.8 1.2 0.5  1.2  0.3 2.1  0.1 0.9 1.1                 --C.sub.6 AlC 2.4 1.5  0.8 1.1 0.4  4.2  0.8 2.2  4.6 0.2 1.1                 M.sub.b       Pd.sub.0.05                                                                       Cr.sub.0.3                                                                         La.sub.0.15                                                                       Ce.sub.0.3                                                                        Ti.sub.0.15                                                                        Zn.sub.0.15                                                                        Al.sub.0.15                                                                       Pd.sub.0.05                                                                        U.sub.0.2                                                                         Cr.sub.0.15                                                                       Ce.sub.0.15         Weight %, MeOH Free Basis                                                     ethanol       10.64                                                                             10.3 10.84                                                                             4.55                                                                              7.69 11.80                                                                              15.0                                                                              8.76 24.5                                                                              8.50                                                                              6.76                acetone       1.22                                                                              3.03 3.01                                                                              --  3.84 1.32 2.50                                                                              1.98 --  2.83                                                                              2.70                iso-C.sub.3 OH                                                                              3.04                                                                              3.03 3.62                                                                              5.37                                                                              2.57 3.09 4.38                                                                              2.54 1.3 3.31                                                                              3.15                n-C.sub.3 OH  14.29                                                                             8.48 9.03                                                                              3.72                                                                              5.77 7.05 13.13                                                                             11.03                                                                              0.4 10.85                                                                             7.21                sec-C.sub.4 OH                                                                              2.13                                                                              6.67 4.22                                                                              6.20                                                                              7.04 1.77 3.75                                                                              3.67 --  4.25                                                                              4.96                iso-C.sub.4 OH                                                                              37.10                                                                             41.20                                                                              42.20                                                                             56.20                                                                             53.90                                                                              32.20                                                                              40.00                                                                             43.00                                                                              6.4 50.00                                                                             49.20               n-C.sub.4 OH  6.68                                                                              7.88 7.83                                                                              7.43                                                                              8.33 6.17 4.38                                                                              7.34 0.5 6.07                                                                              7.66                iso-C.sub.5 OH                                                                              2.13                                                                              0.61 1.20                                                                              --  trace                                                                              2.22 2.50                                                                              1.41 0.8 3.77                                                                              1.80                n-C.sub.5 OH  8.52                                                                              4.25 7.22                                                                              7.02                                                                              trace                                                                              7.48 6.88                                                                              6.78 0.9 6.13                                                                              5.40                iso-C.sub.6 OH                                                                              1.52                                                                              1.21 1.20                                                                              0.41                                                                              5.12 1.32 0.63                                                                              1.41 --  0.94                                                                              1.35                n-C.sub.6 OH  5.48                                                                              4.25 4.82                                                                              4.95                                                                              3.21 5.28 1.88                                                                              5.93 1.3 4.25                                                                              4.96                --C.sub.6 AlC 7.29                                                                              9.10 4.82                                                                              4.54                                                                              2.57 18.50                                                                              5.00                                                                              6.22 59.1                                                                              0.94                                                                              4.96                Iso/Normal Ratio                                                              C.sub.3       .213                                                                              .357 .401                                                                              1.44                                                                              .445 .438 .333                                                                              .230 3.25                                                                              .305                                                                              .437                C.sub.4       5.55                                                                              6.33 5.40                                                                              7.57                                                                              6.48 5.22 9.13                                                                              5.85 12.8                                                                              8.23                                                                              6.43                C.sub.5       0.250                                                                             0.144                                                                              0.166   --   0.297                                                                              0.363                                                                             0.208                                                                              0.89                                                                              0.615                                                                             0.333               C.sub.6       0.277                                                                             0.285                                                                              0.249                                                                             0.083                                                                             1.59 0.250                                                                              0.335                                                                             0.238                                                                              --  0.221                                                                             0.272               overall       0.917                                                                             1.101                                                                              1.097                                                                             1.830                                                                             1.922                                                                              0.982                                                                              1.055                                                                             1.111                                                                              2.75                                                                              1.449                                                                             1.502               __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________    Experiment No.    23  24  25   26  27  28  29  30  31  32  33                 __________________________________________________________________________    M.sub.b           Ca.sub.0.15                                                                       Mo.sub.0.15                                                                       Rh.sub.0.025                                                                       Ce.sub.0.5                                                                        Ce.sub.0.75                                                                       Mn.sub.0.15                                                                       V.sub.0.15                                                                        Ru.sub.0.05                                                                       Rh.sub.0.05                                                                       Re.sub.0.05                                                                       Pt.sub.0.05        Liquid Analysis, Weight %                                                     methanol          84.40                                                                             86.58                                                                             87.78                                                                              86.23                                                                             89.02                                                                             85.52                                                                             91.30                                                                             92.02                                                                             90.95                                                                             91.09                                                                             88.40              ethanol           1.44                                                                              1.59                                                                              1.69 1.55                                                                              2.57                                                                              1.83                                                                              1.09                                                                              2.95                                                                              2.11                                                                              --  2.45               acetone           0.22                                                                              --  0.12 0.25                                                                              0.21                                                                              0.38                                                                              0.41                                                                              0.96                                                                              --  0.84                                                                              0.18               iso-C.sub.3 OH    0.67                                                                              0.64                                                                              0.47 0.46                                                                              0.53                                                                              0.63                                                                              0.44                                                                              --  0.43                                                                              1.38                                                                              0.51               n-C.sub.3 OH      1.26                                                                              1.42                                                                              1.58 1.96                                                                              2.45                                                                              1.43                                                                              0.82                                                                              1.11                                                                              1.36                                                                              0.25                                                                              2.01               sec-C.sub.4 OH    0.50                                                                              0.31                                                                              0.16 0.33                                                                              0.21                                                                              0.53                                                                              0.59                                                                              0.17                                                                              0.18                                                                              0.64                                                                              0.21               iso-C.sub.4 OH    6.32                                                                              6.31                                                                              5.64 6.60                                                                              3.07                                                                              6.05                                                                              4.41                                                                              1.29                                                                              3.47                                                                              0.49                                                                              3.74               n-C.sub.4 OH      0.87                                                                              1.07                                                                              0.87 0.99                                                                              0.58                                                                              1.38                                                                              0.18                                                                              --  0.49                                                                              1.34                                                                              0.73               iso-C.sub.5 OH    0.37                                                                              0.22                                                                              0.05 --  0.07                                                                              --  0.15                                                                              0.18                                                                              0.06                                                                              --  0.18               n-C.sub.5 OH      0.70                                                                              0.94                                                                              0.77 0.85                                                                              0.42                                                                              0.97                                                                              0.17                                                                              0.09                                                                              0.43                                                                              1.13                                                                              0.67               iso-C.sub.6 OH    0.23                                                                              0.20                                                                              0.09 0.10                                                                              0.02                                                                              --  0.12                                                                              0.10                                                                              0.15                                                                              0.62                                                                              0.13               n-C.sub.6 OH      0.32                                                                              0.57                                                                              0.52 0.50                                                                              0.22                                                                              0.56                                                                              0.05                                                                              0.07                                                                              0.23                                                                              1.34                                                                              0.36               C.sub.6 AlC       2.70                                                                              0.15                                                                              0.26 0.19                                                                              0.63                                                                              0.73                                                                              0.27                                                                              1.07                                                                              0.15                                                                              0.90                                                                              0.43               Weight %, MeOH Free Basis                                                     ethanol           9.23                                                                              11.85                                                                             13.83                                                                              11.26                                                                             23.41                                                                             12.64                                                                             12.53                                                                             36.97                                                                             23.31                                                                             --  21.12              acetone           1.41                                                                              --  0.98 1.82                                                                              1.91                                                                              2.62                                                                              4.71                                                                              12.03                                                                             --  9.43                                                                              1.55               iso-C.sub.3 OH    4.29                                                                              4.77                                                                              3.85 3.34                                                                              4.83                                                                              4.35                                                                              5.06                                                                              --  4.75                                                                              15.49                                                                             4.40               n-C.sub.3 OH      8.08                                                                              10.58                                                                             12.93                                                                              14.23                                                                             22.31                                                                             9.88                                                                              9.43                                                                              13.91                                                                             15.03                                                                             2.81                                                                              17.33              M.sub.b           Ca.sub.0.15                                                                       Mo.sub.0.15                                                                       Rh.sub.01025                                                                       Ce.sub.0.5                                                                        Ce.sub.0.75                                                                       Mn.sub.0.15                                                                       V.sub.0.15                                                                        Ru.sub.0.05                                                                       Rh.sub.0.05                                                                       Re.sub.0.05                                                                       Pt.sub.0.05        sec-C.sub.4 OH    3.21                                                                              2.31                                                                              1.31 2.40                                                                              1.91                                                                              3.66                                                                              6.78                                                                              2.13                                                                              1.99                                                                              7.18                                                                              1.81               iso-C.sub.4 OH    40.51                                                                             47.02                                                                             46.15                                                                              47.93                                                                             27.96                                                                             41.78                                                                             50.69                                                                             16.16                                                                             38.34                                                                             5.58                                                                              32.24              n-C.sub.4 OH      5.58                                                                              7.97                                                                              7.12 3.52                                                                              5.28                                                                              9.53                                                                              2.07                                                                              --  5.51                                                                              15.04                                                                             6.29               iso-C.sub.5 OH    2.37                                                                              1.67                                                                              0.41 --  0.64                                                                              --  1.72                                                                              2.26                                                                              0.66                                                                              --  1.55               n-C.sub.5 OH      4.49                                                                              7.00                                                                              6.30 6.17                                                                              3.82                                                                              6.70                                                                              1.95                                                                              1.13                                                                              4.75                                                                              12.68                                                                             5.78               iso-C.sub.6 OH    1.47                                                                              1.49                                                                              0.74 0.73                                                                              0.18                                                                              --  1.38                                                                              1.25                                                                              1.66                                                                              6.96                                                                              1.12               n-C.sub.6 OH      2.05                                                                              4.25                                                                              4.26 3.63                                                                              2.00                                                                              3.87                                                                              0.57                                                                              0.88                                                                              2.54                                                                              15.04                                                                             3.10               C.sub.6 AlC       17.31                                                                             1.11                                                                              2.13 1.38                                                                              5.74                                                                              5.04                                                                              3.10                                                                              13.41                                                                             1.66                                                                              10.10                                                                             3.71               iso/Normal Ratio                                                              C.sub.3           0.531                                                                             0.451                                                                             0.298                                                                              0.235                                                                             0.216                                                                             0.440                                                                             0.537                                                                             0   0.316                                                                             5.51                                                                              0.254              C.sub.4           4.61                                                                              4.57                                                                              5.47 8.10                                                                              3.89                                                                              3.17                                                                              5.73                                                                              7.59                                                                              5.11                                                                              0.248                                                                             3.98               C.sub.5           0.528                                                                             0.239                                                                             0.065                                                                              --  0.167                                                                             --  0.882                                                                             2.97                                                                              0.139                                                                             0   0.268              C.sub.6           0.717                                                                             0.351                                                                             0.174                                                                              0.201                                                                             0.090                                                                             --  2.42                                                                              1.42                                                                              0.654                                                                             0.463                                                                             0.361              overall           1.490                                                                             1.250                                                                             1.118                                                                              1.262                                                                             0.572                                                                             0.997                                                                             1.766                                                                             0.358                                                                             0.855                                                                             0.530                                                                             0.709              __________________________________________________________________________

From the foregoing, it can be seen that alcohol mixtures having a noveldistribution of alcohols as described above are produced by a verysimple and straightforward procedure. Each of these alcohol mixtures canbe directly mixed with gasoline to provide novel alcohol/gasolinecompositions, or, if desired, those alcohol mixtures containing morethan 85% methanol can be fractionally distilled prior to admixing withgasoline to remove excess methanol.

Although only a few embodiments of the present invention have beendescribed above, many modifications can be made without departing fromthe spirit and scope of the invention. All such modifications areintended to be included within the scope of the present invention whichis to be limited only by the following claims.

We claim:
 1. A process for producing a mixture of methanol and higheralcohols comprising contacting a gaseous reactant containing carbonmonoxide and hydrogen at a temperature in the range of 250° to 350° C.and a pressure of no more than 1500 psi with an oxide complex catalystdescribed by the following empirical formula:

    Cu.sub.a ThM.sub.b A.sub.c O.sub.x

wherein M is one or more of Ca, Rh, Pt, Al, La, Re, Ru and Pd; A is analkali metal; andwherein a is 0.5 to 2.5; b is 0.01 to 1.0; c is 0.05 to0.9; and x is a number such that the valence requirements of the otherelements for oxygen is satisfied.
 2. The process of claim 1 wherein theH₂ /CO ratio in said gaseous reactant is from 0.6-6.
 3. The process ofclaim 1 wherein said gaseous reactant is synthesis gas.
 4. The processof claim 1 wherein said reaction is carried out in fixed-bed mode. 5.The process of claim 1 wherein said oxide complex catalyst is preparedby the process comprising:(1) adding an alkali metal carbonate orhydroxide to a solution containing decomposable salts of thorium, copperand "M" to raise the pH of the solution to at least 7.5 and form aprecipitate, (2) heating the precipitate in its mother liquor untilchange in color of said precipitate has ceased, (3) neutralizing themother liquor, (4) recovering the precipitate, and (5) calcining theprecipitate in the presence of an oxygen-containing gas.
 6. The processof claim 5 wherein the pH of the solution in (1) is raised to a pH ofabout 9.3 to about
 10. 7. The process of claim 5 wherein a carbonate isadded in step (1) of the catalyst preparation process, said catalystpreparation process further comprising:(6) contacting said catalyst witha reducing gas while maintaining the temperature of said catalyst belowthe temperature at which significant sintering occurs.
 8. The process ofclaim 1 wherein M is Al, La and/or Pd.